CN102001986A - Method for improving quality of industrial N-methylpyrrolidone - Google Patents
Method for improving quality of industrial N-methylpyrrolidone Download PDFInfo
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- CN102001986A CN102001986A CN2010106025146A CN201010602514A CN102001986A CN 102001986 A CN102001986 A CN 102001986A CN 2010106025146 A CN2010106025146 A CN 2010106025146A CN 201010602514 A CN201010602514 A CN 201010602514A CN 102001986 A CN102001986 A CN 102001986A
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Abstract
The invention discloses a method for improving the quality of industrial N-methylpyrrolidone, comprising the following steps of: taking industrial N-methylpyrrolidone as a raw material, orderly removing amine, cation and anion impurities in the industrial N-methylpyrrolidone with a macroporous absorbent resin column, a strong-acid cation exchange resin column and a strong-base anion exchange resin column which are connected in series to form an ion exchange device, and then rectifying and filtering with a membrane to obtain N-methylpyrrolidone with improved quality. Analysis and detection show that the free amine content (based on methylamine) of the product is smaller than 5ppm, and both the anion impurity content and the cation impurity content meet the requirements on SEMI-C8 standards of chemical material part, established by the Semiconduct or Equipment and Materials International. The ion exchange resin used in the method can be regenerated and reclaimed, has the advantage of low carbon and is environment-friendly. The operation process is simple, and product quality is stable. The method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method that promotes technical grade N-Methyl pyrrolidone quality, be specifically related to a kind of method that technical grade N-Methyl pyrrolidone quality is removed wherein amine, positively charged ion and anionic impurity that promotes.
Background technology
N-Methyl pyrrolidone (NMP) is a kind of important chemical material, is the polar solvent of the strong and good stability of a kind of selectivity, have the boiling point height, nonflammable, toxicity is low, safe in utilization, dissolving power is strong, advantage such as recyclable, biodegradable.It is mainly used in extraction agents such as divinyl, aromatic hydrocarbons, the solvent of many engineering plastics (as poly(vinylidene fluoride) etc.), and the electrode subsidiary material of lithium ion battery, photoresist material remove liquid, and the LCD liquid crystal material is produced, the cleaning of semicon industry wiring board etc.
In the prior art, patent WO03/053924A1 and patent CN1871213A disclose the method for the continuous NMP of preparation respectively.Be raw material promptly with gamma-butyrolactone (GBL), with monomethyl amine (MMA) 320～380 ℃ of temperature, react under the condition of pressure 70～120Pa, reaction product obtains purity greater than 99.5% N-Methyl pyrrolidone after rectifying removes water and monomethyl amine.
In electron trade high-purity N-methyl-2-pyrrolidone is required very highly, need meet the standard of SEMI C8, the purity that promptly requires the NMP product is greater than 99.8%, and metal ion content all should be less than 5ppb mostly.Aforesaid method input cost height, energy consumption is big, and the process control difficulty is dangerous high, is difficult to obtain meeting the product of high-purity N-methyl-2-pyrrolidone requirement, the industrial production of carrying out mass-producing.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that promotes technical grade N-Methyl pyrrolidone quality, specifically provide a kind of method that technical grade N-Methyl pyrrolidone quality is removed wherein amine, positively charged ion and anionic impurity that promotes, the deficiency that exceeds standard with amine, positively charged ion and the negatively charged ion that overcomes in the prior art N-Methyl pyrrolidone.
Technical conceive of the present invention is such:
With the technical grade N-Methyl pyrrolidone is raw material, successively through containing the ion exchange unit that macroporous adsorbent resin, strong acid cation exchange resin column, strongly basic anion exchange resin post are composed in series, remove wherein amine, positively charged ion and anionic impurity, through rectifying, membrane filtration promptly obtains the N-Methyl pyrrolidone of quality-improving.
The method of lifting technical grade N-Methyl pyrrolidone quality of the present invention specifically comprises the steps:
With the technical grade N-Methyl pyrrolidone with the flow velocity of 10 times of column volumes successively by containing the ion exchange unit that macroporous adsorptive resins, strong acid cation exchange resin column and strongly basic anion exchange resin post are composed in series, amine, positively charged ion and anionic impurity in ion-exchange removal N-Methyl pyrrolidone, through rectifying, membrane filtration, promptly obtain the N-Methyl pyrrolidone of quality-improving.
Described macroporous adsorptive resins, strong acid cation exchange resin column and strongly basic anion exchange resin post need carry out pre-treatment before use.Concrete steps are as follows: 1) with the organic alcohols solvent macroporous adsorbent resin is soaked and wash; 2) Zeo-karb is made the transition to behind the H type, with high purity water Zeo-karb is cleaned, cleaning out electrical conductivity of water to resin is 1-10 μ S/cm; 3) anionite-exchange resin is made the transition to behind the OH type, with high purity water anionite-exchange resin is cleaned, cleaning out electrical conductivity of water to resin is 1-10 μ S/cm.
According to the present invention, the strong acid cation exchange resin column, the strongly basic anion exchange resin post that contact with the material N-Methyl pyrrolidone are the high purity quartz material, and storage tank is high-purity perfluorinated material.
The present invention soaks macroporous adsorbent resin and the organic alcohols solvent that washes is small molecules organic alcohols solvent, preferred alcohol or a Virahol.
Behind amine, positively charged ion and the anionic impurity of the present invention in ion-exchange removal technical grade N-Methyl pyrrolidone, under vacuum 25-85kPa condition, carry out rectification under vacuum, cut from 80-120 ℃ of rectifying tower top collection, phlegma is the micro-filtrate membrane filtration of 0.2-1.0 μ m by the aperture, collect, promptly obtain the N-first class pyrrolidone of quality-improving.
During rectifying of the present invention, the material N-Methyl pyrrolidone is from the rectifier charging, and the bottom goes out product, distillates light constituent impurity at cat head, goes out heavy constituent impurity at the tower still, and feed entrance point is apart from least 1 theoretical stage of overhead condenser, and 2 more excellent more than the theoretical stage.Product extraction position is apart from least 1 theoretical stage of tower still reboiler, and 2 more excellent more than the theoretical stage.At least 3 theoretical stages in feed entrance point distance product output position, 4 more excellent more than the theoretical stage.
The N-Methyl pyrrolidone product of the quality-improving that obtains through the inventive method adopts microfiltration membrane to carry out membrane filtration before packing, and microfiltration membrane and shell thereof adopt materials such as solvent-proof PP, PVDF, PTFE, and the aperture of microfiltration membrane is 0.2-1.0 μ m.
The N-Methyl pyrrolidone product that obtains with the inventive method, after testing, unhindered amina (in methylamine) content is less than 5ppm, and anionic impurity content, cation impurity levels all reach the requirement of the chemical material part SEMI C8 standard of semiconductor equipment and material structure formulation.
The present invention's beneficial effect compared with prior art:
The inventive method can effectively be removed amine, positively charged ion and anionic impurity in N-Methyl pyrrolidone and the derived product thereof, and is with low cost, and the ion exchange resin of use can regeneration, low-carbon environment-friendly.
The ion exchange unit operating process that the macroporous adsorbent resin of the inventive method, strong acid cation exchange resin column, strongly basic anion exchange resin post are composed in series is convenient, and constant product quality is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the setting drawing of the inventive method, wherein 1 is technical grade N-Methyl pyrrolidone raw material tank, 2 is transferpump, and 3 is macroporous adsorptive resins, and 4 is strong acid cation exchange resin column, 5 is the strongly basic anion exchange resin post, 6 is transferpump, and 7 is rectifying tower, and 8 is condenser, 9 is film filter, and 10 is the N-Methyl pyrrolidone pan tank.
Embodiment
The invention will be further described below by embodiment, but embodiment does not limit protection scope of the present invention.
Step 1: the pre-treatment of macroporous adsorbent resin, storng-acid cation exchange resin and strongly basic anion exchange resin.
1) pre-treatment of macroporous adsorbent resin: employing organic alcohols solvent (as ethanol, Virahol etc.) soaks polymeric adsorbent and washes, till organic alcohol of resin flushing outlet adds the constant muddiness of water, adopt high purity deionized water that polymeric adsorbent is washed then, till the TOC that cleans water outlet is less than 5.
2) pre-treatment of storng-acid cation exchange resin: Zeo-karb is made the transition to behind the H type, with high purity water Zeo-karb is cleaned, cleaning out electrical conductivity of water until resin is 1-10 μ S/cm.
3) pre-treatment of strongly basic anion exchange resin: anionite-exchange resin is made the transition to behind the OH type, with high purity water anionite-exchange resin is cleaned, cleaning out electrical conductivity of water until resin is 1-10 μ S/cm.
To be respectively charged into the ion exchange column of Φ 60 * 900 through the above-mentioned resin that pre-treatment obtains, be composed in series the ion exchange unit (referring to Fig. 1) that contains macroporous adsorptive resins, strong acid cation exchange resin column and strongly basic anion exchange resin post.
Step 2: with the technical grade N-Methyl pyrrolidone with the flow velocity of 10 times of column volumes successively by macroporous adsorptive resins, strong acid cation exchange resin column and strongly basic anion exchange resin post after the step 1 pre-treatment, the N-Methyl pyrrolidone that obtains is detected, and analytical results is referring to table 1.
Step 3: will carry out rectification under vacuum under vacuum tightness 20-85kPa condition through the N-Methyl pyrrolidone that step 2 obtains, and detect, the N-Methyl pyrrolidone product purity that obtains is greater than 99.8%, and water-content is less than 300ppm.
Step 4: after the N-Methyl pyrrolidone product condensation that obtains after above-mentioned steps three rectifications under vacuum, be the PVDF micro-filtrate membrane filtration of 0.2-1.0 μ m by the aperture, in the N-Methyl pyrrolidone that obtains greater than 0.5 μ m granule number less than 8/ml.
Embodiment 2
Macroporous adsorbent resin, storng-acid cation exchange resin and strongly basic anion exchange resin are carried out pre-treatment, polymeric adsorbent is soaked and wash with organic alcohols solvent Virahol, all the other steps are identical with embodiment 1.
The standard and the analytical results of table 1N-methyl-2-pyrrolidone
| Project | Unit | SEMI C8 | Embodiment | 1 | Embodiment 2 |
| NMP content | wt％ | ?99.80 | 99.82 | 99.89 | |
| Outward appearance | APHA | ?≤30 | 15 | 17 | |
| Water-content (H 2O) | ％ | ?≤0.03 | 0.015 | 0.013 | |
| Unhindered amina (as CH 3NH 2) | ppm | ≤5 | 3 | 3 | |
| Muriate (Cl) | ppb | ≤300 | 119 | 117 | |
| Nitrate (NO 3) | ppb | ≤400 | 230 | 255 | |
| Phosphoric acid salt (PO 4) | ppb | ≤250 | 111 | 114 | |
| Vitriol (SO 4) | ppb | ≤250 | 125 | 122 | |
| Aluminium (Al) | ppb | ≤5 | 0.02 | 0.02 | |
| Antimony (Sb) | ppb | ≤10 | 4 | 3 | |
| Arsenic (As) | ppb | ≤10 | 4 | 5 |
| Arsenic and antimony (as As) | ppb | --- | --- | --- |
| Boron (B) | ppb | ≤10 | 5 | 5 |
| Cadmium (Cd) | ppb | --- | --- | --- |
| Calcium (Ca) | ppb | ≤5 | 1.3 | 1.1 |
| Chromium (Cr) | ppb | ≤10 | 3 | 3 |
| Cobalt (Co) | ppb | --- | --- | --- |
| Copper (Cu) | ppb | ≤5 | 2.2 | 2.6 |
| Gold (Au) | ppb | ≤5 | 2.3 | 2.5 |
| Iron (Fe) | ppb | ≤10 | 6.0 | 6.2 |
| Plumbous (Pb) | ppb | ≤5 | 3.1 | 3.4 |
| Lithium (Li) | ppb | --- | --- | --- |
| Magnesium (Mg) | ppb | ≤5 | 3.1 | 2.9 |
| Manganese (Mn) | ppb | ≤5 | 2.5 | 2.5 |
| Nickel (Ni) | ppb | ≤5 | 2 | 2 |
| Potassium (K) | ppb | ≤5 | 2 | 2 |
| Silver (Ag) | ppb | --- | --- | --- |
| Sodium (Na) | ppb | ≤10 | 4 | 4 |
| Strontium (Sr) | ppb | --- | --- | --- |
| Tin (Sn) | ppb | ≤5 | Do not detect | Do not detect |
| Titanium (Ti) | ppb | ≤5 | Do not detect | Do not detect |
| Vanadium (V) | ppb | --- | --- | --- |
| Zinc (Zn) | ppb | ≤10 | 5 | 6 |
| Dust granules/ml | ≥0.5μm | ≤15 | 8 | 8 |
Above-mentioned analytical procedure, colourity is reference colour with platinum-cobalt reference liquid, analyzes with visual colorimetry; NMP content adopts gas chromatographic analysis; Water-content adopts the analysis of karl Fischer method; Residue on evaporation is analyzed with weighting method; Positively charged ion adopts plasma mass spectrum (ICP-MS) analysis; Negatively charged ion adopts ion-exchange chromatogram analysis; The title of testing tool and model are referring to table 2.
The title of table 2 testing tool and model
More than specific embodiments of the invention are described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, not breaking away from impartial conversion and the modification of being done under the spirit and scope of the present invention, all should contain within the scope of the invention.
Claims (7)
1. a method that promotes technical grade N-first class pyrrolidone quality is characterized in that, comprises the steps:
With the technical grade N-Methyl pyrrolidone with the flow velocity of 10 times of column volumes successively by containing the ion exchange unit that macroporous adsorptive resins, strong acid cation exchange resin column and strongly basic anion exchange resin post are composed in series, amine, positively charged ion and anionic impurity in ion-exchange removal N-Methyl pyrrolidone, through rectifying, membrane filtration, promptly obtain the N-Methyl pyrrolidone of quality-improving.
2. method according to claim 1 is characterized in that, described macroporous adsorptive resins, strong acid cation exchange resin column, strongly basic anion exchange resin post need carry out pre-treatment before use.
3. method according to claim 2 is characterized in that, described pre-treatment step is as follows:
1) with the organic alcohols solvent macroporous adsorbent resin is soaked and wash;
2) Zeo-karb is made the transition to behind the H type, with high purity water Zeo-karb is cleaned, cleaning out electrical conductivity of water to resin is 1-10 μ S/cm;
3) anionite-exchange resin is made the transition to behind the OH type, with high purity water anionite-exchange resin is cleaned, cleaning out electrical conductivity of water to resin is 1-10 μ S/cm.
4. method according to claim 3 is characterized in that, described organic alcohols solvent is the small molecular alcohol kind solvent.
5. method according to claim 4 is characterized in that, described small molecular alcohol kind solvent is ethanol or Virahol.
6. method according to claim 1, it is characterized in that, the step of described rectifying, membrane filtration is as follows: will carry out rectification under vacuum under vacuum 25-85kPa condition through the N-Methyl pyrrolidone of ion-exchange, cut from 80-120 ℃ of rectifying tower top collection, through condensation, phlegma is the micro-filtrate membrane filtration of 0.2-1.0 μ m by the aperture, collects, and promptly obtains the N-first class pyrrolidone of quality-improving.
7. method according to claim 1 is characterized in that, the highly acidic cation ion exchange resin column, the strongly basic anion exchange resin post that contact with the material N-Methyl pyrrolidone are the high purity quartz material, and storage tank is high-purity perfluorinated material.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058910A (en) * | 2013-01-21 | 2013-04-24 | 郑州大学 | Separation method of organic amine impurity in N-methyl pyrrolidinone |
| CN103214356A (en) * | 2013-04-12 | 2013-07-24 | 西陇化工股份有限公司 | Glutaraldehyde refining method |
| CN109912485A (en) * | 2019-04-09 | 2019-06-21 | 慈溪市赛思德环保科技有限公司 | A kind of method and system of NMP waste liquid purification |
| CN111138336A (en) * | 2019-12-31 | 2020-05-12 | 江苏中德电子材料科技有限公司 | Efficient, energy-saving and environment-friendly continuous production process of ultra-clean high-purity N-methyl pyrrolidone |
| CN111467874A (en) * | 2019-01-24 | 2020-07-31 | 仓敷纤维加工株式会社 | Method for filtering medical liquid containing carboxylic acid derivative |
| CN113354568A (en) * | 2021-06-28 | 2021-09-07 | 合肥中聚合臣电子材料有限公司 | Method for ultimate water removal of electronic-grade N-methyl pyrrolidone |
| CN113429329A (en) * | 2021-07-06 | 2021-09-24 | 镇江润晶高纯化工科技股份有限公司 | Purification method of semiconductor grade N-methyl pyrrolidone |
| CN115160225A (en) * | 2022-09-01 | 2022-10-11 | 阜新泽程化工有限责任公司 | Industrial production method of electronic pure pyrazole |
| CN117510390A (en) * | 2024-01-08 | 2024-02-06 | 江苏天鹏电源有限公司 | Method and system for removing free ammonia in NMP |
| CN117534235A (en) * | 2023-11-15 | 2024-02-09 | 重庆中润新材料股份有限公司 | NMP waste liquid treatment system, method, equipment and medium |
| CN118059833A (en) * | 2024-04-17 | 2024-05-24 | 天津赛飞乐生物技术有限公司 | Preparation method and application of surface modified ion exchange type limited-access microporous material |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058910B (en) * | 2013-01-21 | 2014-09-17 | 郑州大学 | Separation method of organic amine impurity in N-methyl pyrrolidinone |
| CN103058910A (en) * | 2013-01-21 | 2013-04-24 | 郑州大学 | Separation method of organic amine impurity in N-methyl pyrrolidinone |
| CN103214356A (en) * | 2013-04-12 | 2013-07-24 | 西陇化工股份有限公司 | Glutaraldehyde refining method |
| CN111467874A (en) * | 2019-01-24 | 2020-07-31 | 仓敷纤维加工株式会社 | Method for filtering medical liquid containing carboxylic acid derivative |
| CN111467874B (en) * | 2019-01-24 | 2023-02-28 | 仓敷纤维加工株式会社 | Method for filtering medical liquid containing carboxylic acid derivative |
| CN109912485A (en) * | 2019-04-09 | 2019-06-21 | 慈溪市赛思德环保科技有限公司 | A kind of method and system of NMP waste liquid purification |
| CN109912485B (en) * | 2019-04-09 | 2024-05-31 | 慈溪市赛思德环保科技有限公司 | NMP waste liquid purification method and system |
| CN111138336A (en) * | 2019-12-31 | 2020-05-12 | 江苏中德电子材料科技有限公司 | Efficient, energy-saving and environment-friendly continuous production process of ultra-clean high-purity N-methyl pyrrolidone |
| CN113354568B (en) * | 2021-06-28 | 2024-04-12 | 合肥中聚和成电子材料有限公司 | Method for limiting water removal of electronic grade nitrogen methyl pyrrolidone |
| CN113354568A (en) * | 2021-06-28 | 2021-09-07 | 合肥中聚合臣电子材料有限公司 | Method for ultimate water removal of electronic-grade N-methyl pyrrolidone |
| CN113429329A (en) * | 2021-07-06 | 2021-09-24 | 镇江润晶高纯化工科技股份有限公司 | Purification method of semiconductor grade N-methyl pyrrolidone |
| CN115160225A (en) * | 2022-09-01 | 2022-10-11 | 阜新泽程化工有限责任公司 | Industrial production method of electronic pure pyrazole |
| CN117534235A (en) * | 2023-11-15 | 2024-02-09 | 重庆中润新材料股份有限公司 | NMP waste liquid treatment system, method, equipment and medium |
| CN117510390B (en) * | 2024-01-08 | 2024-03-29 | 江苏天鹏电源有限公司 | Method and system for removing free ammonia in NMP |
| CN117510390A (en) * | 2024-01-08 | 2024-02-06 | 江苏天鹏电源有限公司 | Method and system for removing free ammonia in NMP |
| CN118059833A (en) * | 2024-04-17 | 2024-05-24 | 天津赛飞乐生物技术有限公司 | Preparation method and application of surface modified ion exchange type limited-access microporous material |
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Application publication date: 20110406 |